Adsorption and capillary condensation in porous media: Liquid retention and interfacial configurations in angular pores

Conventional models Of liquid distribution, flow, and solute transport in partially saturated porous media are limited by the representation of media pore space as a bundle of cylindrical capillaries (BCC). Moreover, the capillary model ignores the dominant contribution of adsorptive surface forces and liquid films at low potentials. We propose two new complementary elements for improving our understanding of liquid configuration in porous media: (1) an approach for considering the individual contributions of adsorptive and capillary forces to the matric potential and (2) a more realistic model for pore space geometry. Modern interface science formalism is applied to determine the thickness of adsorbed liquid films as a function of thermodynamic conditions and specific surface area of the medium. The augmented Young-Laplace (AYL) equation provided the necessary framework for combining adsorptive and capillary processes. A new pore space geometry composed of an angular pore cross section (for capillary processes) connected to slit-shaped spaces with internal surface area (for adsorption processes) offers a more realistic representation of natural porous media with explicit consideration of surface area (absent in the standard BCC model). Liquid-vapor configuration, saturation, and liquid-vapor interfacial area were calculated for different potentials and pore (unit cell) dimensions. Pore dimensions may be easily related to measurable soil properties such as specific surface area and porosity. Rigorous calculations based on the AYL equation were simplified and led to the development of algebraic expressions relating saturation and interfacial area of liquid in the proposed pore space geometry to chemical potential. These simple expressions are amenable to upscaling procedures similar to those presently used with the BCC model.